Fourteen phenolic acids have been selectively determined in olive-oil samples using the co-electrosmotic capillary electrophoresis mode with UV detection after the LLE extraction system. A polycationic surfactant (hexadimetrine bromide, HDB), which dynamically coats the inner surface of the capillary and causes a fast anodic electroosmotic flow, was added to the electrolyte. The main factors affecting co-electroosmotic flow (EOF) such as type of modifier, concentration, and influence of organic solvents have been studied. Other parameters such as pH, type, and concentration of buffer, applied voltage, and injection time were also optimised using hydrodynamic injection for 8 s and UV detection at 210 nm. The composition optimum of the running buffer used was a 20% 2-propanol, 0.001% HDB, and 50 mM sodium borate at a pH value of 9.6. The method has been applied to determination and quantification of fourteen phenolic acids at ppb levels in olive oil samples after a liquid-liquid extraction.